Anionic Cu - American Chemical Society

Dec 29, 2007 - Department of Chemistry, Shantou UniVersity, Guangdong 515063, People's Republic of China. ReceiVed July 11, 2007; ReVised Manuscript ...
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CRYSTAL GROWTH & DESIGN

Anionic CunIn Cluster-Based Architectures Induced by In Situ Generated N-Alkylated Cationic Triazolium Salts

2008 VOL. 8, NO. 2 568–574

Tao Wu, Mian Li, Dan Li,* and Xiao-Chun Huang* Department of Chemistry, Shantou UniVersity, Guangdong 515063, People’s Republic of China ReceiVed July 11, 2007; ReVised Manuscript ReceiVed September 28, 2007

ABSTRACT: Five new copper(I) iodide coordination polymers, (Cu10I10)(Cu6I6)[(Cu(Bta)2]3- · (DMBta)4+ · (I-) · x(I2) (x ≈ 1.5) (1), [Cu2I2(MBta)] (2), [Cu2I2(MTa)] (3), (Cu5I5)[Cu(Ta)2]- · (DETa)+ (4), and [Cu3I(Bta)2] (5) (Bta ) benzotriazole, DMBta ) 1,3-N-dimethylbenzotriazolium, MBta ) 1-N-methylbenzotriazole, MTa ) 1-N-methyltriazole, Ta ) 1,2,3-triazole, DETa ) 1,3N-diethyltriazolium), have been prepared by the solvo(hydro)thermal reactions of CuI, KI, and benzotriazole (or 1,2,3-triazole) in methanol (or ethanol or water) and structurally characterized. Complex 1 shows a highly unusual two-dimensional (2D) f threedimensional (3D) interpenetrated anionic network containing two new discrete neutral Cu10I10/Cu6I6 cluster units, and complex 4 consists of 2D anionic layers with Cu5I5 cluster units, both of which involve in situ di-N-alkylated cationic triazolium to induce the anionic frameworks. Complexes 2 and 3 both contain neutral in situ mono-N-alkylated ligands and exhibit similar one-dimensional (1D) double-stranded stairlike ribbon structures. Complex 5 exhibits a 2D simple sheet structure containing nonalkylated Btaligands. A mechanism of the solvo(hydro)thermal reaction is proposed. As evidenced by means of electrospray ionization mass spectrometry measurements, a simultaneous redox, N-alkylated and self-assembly reaction occurs. Introduction Copper(I) halides have been employed and systematically investigated as inorganic components in the construction of inorganic–organic hybrid coordination polymers, which lies at the frontier of crystal engineering.1–4 In particular, the structural variation of copper(I) iodide aggregates, ranging from discrete oligomers2 to polymeric chains3 and two-dimensional (2D) layers,4 is due to the strongly coordinating nature of the iodide anion, which can bridge two or more copper centers, giving various species of the form [(CuxIy)x-y]n. Among these copper(I) iodide motifs, discrete neutral CunIn clusters are facile acting as secondary building units (SBUs) for constructing multidimensional coordination frameworks.5–8 Compared with those commonly reported ones such as Cu2I2 rhomboid dimers6 and Cu4I4 cubane tetramers,7 coordination architectures constructed by discrete high-nuclear CunIn clusters (n > 4) have rarely been documented previously.8 Most of the reported copper(I)-iodide cluster-based frameworks are neither cationic nor anionic but neutral.5–8 A rational consideration for constructing charged frameworks is to introduce templates with opposite charges to direct the selfassembly.9 For example, the organic cations have been widely utilized as templates of pores or intercalary guests of interlayers in the preparation of zeolites and inorganic materials,10 where the organic cations not only contribute to enlarge the porous size, but also direct the formation of the anionic frameworks. However, little attention has been drawn to the application of in situ generated organic cations to fabricate charged frameworks. As our continuous research on the solvothermal syntheses of new copper(I) halides complexes,11 we adopted a synthetic approach by introducing organic cationic triazolium salts to the self-assembly processes and report herein a range of anionic copper(I)-iodide cluster-based coordination polymers. We chose multidentate triazole as a precursor to in situ generate Nalkylated cationic triazolium by the solvothermal reaction of triazole and methanol (or ethanol) induced by nucleophilic * To whom correspondence should be addressed. E-mail: [email protected]; [email protected].

haloid ions.12 As will be seen, the di-N-alkylated triazolium organic cations practically induce the formation of multidimensional anionic frameworks as observed in(Cu10I10)(Cu6I6)[(Cu(Bta)2]3- · (DMBta)4+ · (I-) · x(I2) (x ≈ 1.5) (1) and (Cu5I5)[Cu(Ta)2]- · (DETa)+ (4). Interestingly, complex 1 exhibits a novel two-dimensional (2D) f three-dimensional (3D) interpenetrated network with two new discrete neutral Cu10I10/ Cu6I6 clusters as SBUs, and complex 4 consists of a 2D layer structure containing Cu5I5 cluster units. The reaction of CuI, KI, and benzotriazole in methanol produces not only complex 1 but a minor product [Cu2I2(MBta)] (2), which has a structure similar to[Cu2I2(MTa)] (3) of a one-dimensional (1D) doublestranded stairlike ribbon containing neutral in situ formed monoN-alkylated ligands. In contrast, the reaction with the nonalkylated Bta- ligand in water results in a neutral 2D simple sheet structure [Cu3I(Bta)2] (5). Experimental Section Materials and Physical Measurements. All reagents were of analytical grade and used as obtained from commercial sources without further purification. Infrared spectra were obtained in KBr pellets in the range of 4000–400 cm-1 on a Nicolet Avatar 360 FT-IR spectrometer. Thermogravimetric analysis (TGA) was carried out under argon atmosphere with the heating rate of 10 °C/min from room temperature to 800 °C on a Seiko Extar 6000 TG/DTA equipment. Electrospray ionization mass spectrometry (ESI-MS) analyses were carried out using a Thermo LCQ DECA XP liquid chromatography– mass spectrometry. X-ray photoemission spectroscopy (XPS) measurements were performed at a base pressure of 10-8 Torr under Mg KR (1253.6 eV) primary radiation (14 kV, 15 mA) on a Kratos XSAM 800 instrument. Syntheses. (Cu10I10)(Cu6I6)[(Cu(Bta)2]-3 · (DMBta)+4 · (I-) · x(I2) (x ≈ 1.5) (1) and [Cu2I2(MBta)] (2). A mixture of CuI (0.190 g, 1.0 mmol), KI (0.166 g, 1.0 mmol), benzotriazole (0.132 g, 1.0 mmol), and methanol (8.0 mL) was stirred for 2 min in air, then transferred and sealed in a 25 mL Teflon-lined reactor. The reactor was heated in an oven to 140 °C for 72 h and then cooled to room temperature at a rate of 5 °C h-1. Yellow-green columnar crystals of 1 were obtained as major products (0.064 g, 24.3% based on CuI), accompanied by orange crystals of minor product 2. IR data (KBr, cm-1): 1 ν(C-N) 1326 s; 2 ν(C-N) 1322 s. The formula of complex 1 was further conformed by XPS and TGA.

10.1021/cg070639f CCC: $40.75  2008 American Chemical Society Published on Web 12/29/2007

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Table 1. Crystallographic and Structure Refinement Parameter for 1, 3–5 empirical formula formula weight crystal system space group a/Å b/Å c/Å R/° β/° γ/° V/Å3 Z dcalcd/g · cm3 T/K µ/mm-1 reflection collected unique data R(int) GOF R1, wR2 [I > 2 σ(I)]a R1, wR2 (all data)a

1

3

4

5

C68H64N30Cu19I20 5046.75 tetragonal P42/ncm 28.4132(7) 28.4132(7) 14.0586(7) 90 90 90 11349.6(7) 4 2.954 293(2) 8.967 69177 6951 0.0434 1.097 0.0559, 0.1596 0.0704, 0.1698

C3H5N3Cu2I2 463.98 triclinic P1j 7.9605(5) 8.2819(6) 8.3378(6) 116.3220(10) 99.5430(10) 104.1530(10) 453.34(5) 2 3.399 293(2) 11.433 3120 1561 0.0306 1.107 0.0380, 0.1023 0.0395, 0.1038

C10H16N9Cu6I5 1278.06 monoclinic P21/c 10.6931(10) 14.4122(15) 17.5869(17) 90 102.795(2) 90 2643.0(4) 4 3.212 293(2) 10.599 12091 5843 0.0400 0.972 0.0617, 0.1478 0.1121, 0.1778

C12H8Cu3N6I 553.76 orthorhombic Pnma 11.6390(7) 29.7697(19) 4.1222(3) 90 90 90 1428.30(16) 4 2.575 293(2) 6.590 11114 1722 0.0287 1.177 0.0486, 0.1283 0.0615, 0.1434

a R1 ) [Σ(Fo| - |Fc)/Fo|. wR2 )[Σw(Fo2 - Fc2)2/Σw(Fo2)2]1/2. w ) 1/[σ2(Fo2) + (0.0876P)2 + 103.9405P] for 1, w ) 1/[σ2(Fo2) + 0.0662P)2 + 0.4282P] for 3, w ) 1/[σ2(Fo2) + (0.0941P)2 + 0.0000P] for 4, w ) 1/[σ2(Fo2) + (0.0860P)2 + 1.6555P] for 5, where P ) (Fo2 + 2Fc2)/3.

[Cu2I2(MTa)] (3). The preparation is analogous to 1 except substituting benzotriazole with 1,2,3-triazole. Grey platelet crystals were obtained (0.087 g, 18.9% based on HTa). IR data (KBr, cm-1): ν(C-N) 1300 s. (Cu5I5)[Cu(Ta)2]- · (DETa)+ (4). The preparation is analogous to 3 except substituting methanol with ethanol. Pale-yellow crystals were obtained (0.065 g, 10.3% based on HTa). IR data (KBr, cm-1): ν(C-N) 1302 s. [Cu3I(Bta)2] (5). The preparation is analogous to 1 except substituting methanol with water (10 mL). Pale-yellow prismatic crystals were obtained (0.058 g, 21.3% based on HBta). IR data (KBr, cm-1): 1460 vs, 1382 s, 1204 s, 1013 s, 882 m, 743 s. X-ray Crystallography. Intensity data were collected on a Bruker Smart Apex CCD diffractometer by graphite-monochromated Mo KR (λ ) 0.71073 Å) radiation using the ω-2θ scan method at room temperature. The structures were solved with the direct method and refined on F2 by full-matrix least-squares technique using the SHELXTL program package.13 Anisotropic thermal parameters were applied to all nonhydrogen atoms. The hydrogen atoms were generated geometrically (C-H ) 0.960 Å). The crystallographic calculations were conducted using the SHELXL-97 program package. Crystallographic data are summarized in Table 1. Selected bond lengths and bond angles are listed in Table 2.

Results and Discussion Syntheses. As shown in Scheme 1, the reaction of benzotriazole with CuI, KI in a molar ratio of 1:1:1 in methanol yielded yellow-green columnar crystals (Cu10I10)(Cu6I6)[(Cu(Bta)2]3- · (DMBta)4+ · (I-) · x(I2) (x ≈ 1.5) (1), as a major product, and orange prismatic crystals [Cu2I2(MBta)] (2), as a minor product. Mono-N-methylated and di-N-methylated products were found in the complexes and residual solution (Figure S1a, Supporting Information). Unfortunately, the reaction of benzotriazole and ethanol formed a mixed colloid residue that was difficult to characterize, and no single crystal was obtained. However, ESI-MS analysis confirmed that alkylated compounds EBta and DEBta did exist in the reaction filtrate (Figure S1b, Supporting Information). In contrast, the substitution of methanol with water in the same conditions yielded complex [Cu3I(Bta)2] (5). When benzotriazole was replaced by 1,2,3triazole, we also obtained two other coordination polymers [Cu2I2(MTa)] (3) and (Cu5I5)[Cu(Ta)2]- · (DETa)+ (4) in methanol and ethanol, respectively. Although only 3 contained coordinated alkylated compounds, mono- and di-N-alkylated heterocycles (MTa and DMTa; ETa and DETa) were identified

in both reaction filtrates (Figure S1d,e, Supporting Information). ESI-MS analyses also confirmed that various corresponding mono- and dialkylated heterocycles existed in the reaction filtrates of other azole compounds such as benzimidazole and 1,2,4-triazole with bromide salt (Figure S1f-j, Supporting Information). Some comparative experiments had been attempted by changing the molar ratio of the starting materials and the reaction temperatures, and unfortunately, no suitable single crystals were obtained. Interestingly, the addition of a small amount of amylum solution to the reaction filtrates of 1-4 resulted in a color change from orange or brown to dark blue, implying the presence of iodine in the filtrates. However, no iodine was found in the reaction without CuI despite the formation of N-alkylated compounds identified by ESI-MS (Figure S1c, Supporting Information). These findings indicated that the self-assemblies of 1-4 involved the oxidation of iodide to iodine. Although the reactions in sealed reactors were complicated, either of the two possible processes should exist: (i) CuII intermediate (X) was formed by the reaction of CuI and oxygen and then oxidized iodide to iodine; (ii) CuI intermediate (X) was formed directly by the reaction of CuI and oxygen generating CuI and iodine. On the basis of the above ESI-MS evidence and hypothesis, the mechanism of these solvothermal reactions is tentatively suggested as follows (Scheme 2): RI (R ) -CH3 or -C2H5), formed by the reversible nucleophilic substitution reaction of ROH and iodide ions under high temperature and autogenous pressure, reacts with benzotriazole or triazole to simultaneously produce mono- and di-N-alkylated heterocycles. The reactants and in situ N-alkylated ligands self-assemble to produce different coordination polymers by the effects of kinetic and thermodynamic stabilities. The solvothermal reactions are simultaneous redox, N-alkylated and self-assembly processes, resembling the situation previously reported by Yao et al.12b Structures. Single-crystal X-ray crystallography shows that complexes 1-4 all contain mono- or di-N-alkylated triazolium [N-C 1.44062(1)–1.46245(4) Å].14 The FT-IR spectra of complexes 1-4 in the solid state also confirm the formation of in situ N-alkylated ligands by the observation of strong absorption at 1330–1300 cm-1 for the ν(Ar)N-C(R) stretching vibration.

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Table 2. Selected Bond Lengths (Å) and Angles (°) for 1,a 3,b 4,c and 5d complex 1 I(1)-Cu(1) I(1)-Cu(3) I(2)-Cu(2) I(2)-Cu(2)#2 I(2)-Cu(1)#1 I(2)-Cu(1) I(3)-Cu(1) I(3)-Cu(3)#1 I(3)-Cu(2) I(4)-Cu(9)#3 I(4)-Cu(5) I(4)-Cu(8)#3 I(5)-Cu(8)#3 I(5)-Cu(8) I(5)-Cu(5)#1 I(5)-Cu(5) I(6)-Cu(9) I(6)-Cu(9)#3 I(6)-Cu(5) I(6)-Cu(5)#1 I(7)-Cu(3)#1 I(7)-Cu(3) Cu(5)-N(1) Cu(5)-Cu(9)#3 Cu(5)-Cu(8)#3 Cu(1)-N(3) Cu(1)-Cu(3)#1 Cu(4)-N(2)#1 Cu(4)-N(2) Cu(2)-I(3)#5 Cu(2)-I(2)#2

2.6676(15) 2.8469(16) 2.6570(15) 2.6570(15) 2.8055(17) 2.8055(17) 2.5776(14) 2.6044(15) 2.6411(15) 2.613(5) 2.6254(14) 2.644(5) 2.529(2) 2.529(2) 2.7356(16) 2.7356(16) 2.508(3) 2.508(3) 2.7099(16) 2.7099(16) 2.6056(16) 2.6056(16) 1.992(7) 2.676(4) 2.678(3) 2.006(7) 2.976(2) 1.878(7) 1.878(7) 2.6411(15) 2.6570(15)

I(1)-Cu(2) I(1)-Cu(1) I(2)-Cu(1) I(2)-Cu(2) I(2)-Cu(2)#2 Cu(1)-N(2) Cu(1)-Cu(1)#1 Cu(1)-I(1)#1 Cu(1)-Cu(2) Cu(2)-N(3)#1 Cu(2)-I(2)#2 N(1)-C(3)

2.6883(10) 2.7063(11) 2.6024(9) 2.6318(10) 2.6760(10) 2.052(5) 2.6430(18) 2.6915(10) 2.8762(12) 2.053(6) 2.6760(10) 1.453(10)

N(3)-Cu(1)-I(3) N(3)-Cu(1)-I(1) I(3)-Cu(1)-I(1) N(3)-Cu(1)-I(2) I(3)-Cu(1)-I(2) I(1)-Cu(1)-I(2) I(3)-Cu(2)-I(3)#5 I(3)-Cu(2)-I(2) I(3)#5-Cu(2)-I(2) I(3)-Cu(2)-I(2)#2 I(3)#5-Cu(2)-I(2)#2 I(2)-Cu(2)-I(2)#2 N(7)-Cu(3)-I(3)#1 N(7)-Cu(3)-I(7) I(3)#1-Cu(3)-I(7) N(7)-Cu(3)-I(1) I(3)#1-Cu(3)-I(1) I(7)-Cu(3)-I(1) N(2)#1-Cu(4)-N(2) N(1)-Cu(5)-I(4) N(1)-Cu(5)-I(6) I(4)-Cu(5)-I(6) N(1)-Cu(5)-I(5) I(4)-Cu(5)-I(5) I(6)-Cu(5)-I(5) N(8)-Cu(6)-N(8)#6 I(5)#3-Cu(8)-I(5) I(5)#3-Cu(8)-I(4)#3 I(5)-Cu(8)-I(4)#3 I(6)-Cu(9)-I(4)#3 I(6)#3-Cu(9)-I(4)#3 complex 3 N(2)-Cu(1)-I(2) N(2)-Cu(1)-I(1)#1 I(2)-Cu(1)-I(1)#1 N(2)-Cu(1)-I(1) I(2)-Cu(1)-I(1) I(1)#1-Cu(1)-I(1) N(3)#1-Cu(2)-I(2) N(3)#1-Cu(2)-I(2)#2 I(2)-Cu(2)-I(2)#2 N(3)#1-Cu(2)-I(1) I(2)-Cu(2)-I(1) I(2)#2-Cu(2)-I(1)

complex 4 121.9(2) 106.3(2) 115.61(5) 105.5(2) 105.23(5) 99.40(5) 105.98(8) 107.75(2) 113.99(2) 113.99(2) 107.75(2) 107.55(8) 112.2(2) 110.0(2) 118.71(6) 97.7(2) 108.95(5) 107.06(5) 177.4(5) 118.9(2) 107.6(2) 111.66(5) 103.7(2) 112.28(5) 101.01(5) 180.000(1) 122.29(18) 118.77(9) 118.77(9) 119.09(10) 119.09(1)

C(9)-N(9) I(1)-Cu(2) I(1)-Cu(1) I(1)-Cu(6) I(1)-Cu(5) I(5)-Cu(6)#1 I(5)-Cu(4) I(5)-Cu(1) I(5)-Cu(3) I(5)-Cu(2) I(3)-Cu(2) I(3)-Cu(3) I(4)-Cu(6) I(4)-Cu(2) I(2)-Cu(1) I(2)-Cu(3) Cu(1)-N(1) Cu(3)-N(6) Cu(4)-N(2) Cu(4)-I(4)#1 Cu(4)-Cu(6)#1 Cu(4)-Cu(2)#1 Cu(4)-I(3)#1 Cu(5)-N(3)#4 Cu(5)-N(4)#2

1.444(17) 2.6211(19) 2.6888(19) 2.726(2) 2.881(3) 2.725(2) 2.737(2) 2.778(2) 2.825(2) 2.869(2) 2.617(2) 2.6949(19) 2.583(2) 2.692(2) 2.584(2) 2.584(2) 2.014(10) 2.014(10) 1.975(10) 2.573(2) 2.668(3) 2.722(3) 2.749(3) 1.915(10) 1.924(10)

128.45(16) 98.50(16) 106.62(4) 96.34(17) 107.04(3) 121.37(3) 119.00(17) 103.24(15) 118.41(3) 100.19(15) 106.72(3) 107.37(4)

I(1)-Cu(1)#1 I(1)-Cu(1) I(1)-Cu(1)#2 I(1)-Cu(1)#3 Cu(2)-N(2) Cu(2)-N(2)#1 Cu(1)-N(1) Cu(1)-N(3)#4 Cu(1)-I(1)#5 N(3)-Cu(1)#6

2.7620(8) 2.7620(8) 2.8036(8) 2.8036(8) 1.906(4) 1.906(4) 1.943(3) 1.944(4) 2.8036(8) 1.944(4)

N(1)-Cu(1)-I(2) N(1)-Cu(1)-I(1) I(2)-Cu(1)-I(1) N(1)-Cu(1)-I(5) I(1)-Cu(1)-I(5) I(3)-Cu(2)-Cu(4)#2 I(3)-Cu(2)-I(5) I(1)-Cu(2)-I(5) I(4)-Cu(2)-I(5) N(6)-Cu(3)-I(2) N(6)-Cu(3)-I(3) I(2)-Cu(3)-I(3) N(6)-Cu(3)-I(5) N(2)-Cu(4)-I(4)#1 N(2)-Cu(4)-I(5) I(4)#1-Cu(4)-I(5) N(2)-Cu(4)-I(3)#1 I(4)#1-Cu(4)-I(3)#1 I(5)-Cu(4)-I(3)#1 N(3)#4-Cu(5)-N(4)#2 N(3)#4-Cu(5)-I(1) I(1)-Cu(5)-I(3)#5 N(5)#2-Cu(6)-I(4) N(5)#2-Cu(6)-I(1) I(4)-Cu(6)-I(1)

116.3(3) 103.9(3) 113.80(7) 98.6(3) 111.59(7) 61.95(7) 112.66(6) 110.79(6) 92.99(6) 118.1(3) 103.6(3) 113.90(7) 98.4(3) 118.9(3) 98.1(3) 14.71(8) 102.8(3) 111.47(8) 109.51(9) 137.7(5) 106.7(3) 97.01(9) 118.8(3) 102.4(3) 110.38(7)

complex 5 Cu(1)#1-I(1)-Cu(1) Cu(1)#1-I(1)-Cu(1)#2 Cu(1)-I(1)-Cu(1)#2 Cu(1)-I(1)-Cu(1)#3 Cu(1)#2-I(1)-Cu(1)#3 N(2)-Cu(2)-N(2)#1 N(1)-Cu(1)-N(3)#4 N(1)-Cu(1)-I(1) N(3)#4-Cu(1)-I(1) N(1)-Cu(1)-I(1)#5

85.20(3) 179.10(2) 95.57(3) 179.10(2) 83.65(3) 159.2(2) 137.49(18) 102.92(12) 107.17(11) 105.24(12)

a Symmetry code: #1 y, x, z; #2 -x + 1, -y + 1, -z; #3 -x + 3/2, -y + 3/2, z; #4 -y + 3/2, -x + 3/2, z; #5 -y + 1, -x + 1, -z; #6 -x + 1, -y + 1, -z + 1. b Symmetry code: #1 -x + 2, -y + 2, -z + 2; #2 -x + 1, -y + 2, -z + 2. c Symmetry code: #1 -x + 2, y + 1/2, -z + 1/2; #2 -x + 2, y - 1/2, -z + 1/2; #3 x, -y + 1/2, z + 1/2; #4 -x + 2, -y + 1, -z; #5 x, -y + 1/2, z - 1/2. d Symmetry code: #1 x, -y + 1/2, z; #2 x, y, z + 1; #3 x, -y + 1/2, z + 1; #4 x + 1/2, y, -z - 1/2; #5 x, y, z - 1; #6 x - 1/2, y, -z - 1/2.

Scheme 1. Syntheses of Complexes 1-5

(Cu10I10)(Cu6I6)[(Cu(Bta)2]3- · (DMBta)4+ · (I-) · x(I2) (x ≈ 1.5) (1). Complex 1 is a 3D coordination polymer constructed by three types of copper(I) SBUs (SBU-I, SBU-II, SBU-III). In SBU-I (Figure 1a), copper(I) atom is coordinated in a nearly linear fashion [N-Cu-N 177.536(5)°, Cu-N 1.87895(6) Å] by two 2-nitrogen atoms from two different Bta- ligands with a dihedral angle of 13.4512(4)°. SBU-II (Figure 1b) consists of 10 copper(I) atoms and 10 iodine atoms, fashioning a “S-shaped double-bowl” arrangement with an inverse center by 13 coedge

Scheme 2. Suggested Mechanism of the Solvothermal Reaction

Cu2I2 rhomboids [Cu-I 2.60104(8) –2.84822(9) Å, Cu · · · Cu 2.97524(9)–3.2178(1) Å]. The distorted tetrahedral geometry

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Figure 1. Complex 1: (a) SBU-I: [Cu(Bta)2]-, (b) SBU-II: Cu10I10 cluster, (c) SBU-III: Cu6I6 cluster, Cu(8) and Cu(9) locate at two disorder positions (purple, I; red, Cu; blue, N).

Figure 3. Complex 1: (a) 1D nanochannel filled with iodine atoms (green) along the c-direction, (b) π · · · π interaction between DMBta+ guest cations (orange) and Bta- ligand (green).

Figure 2. Complex 1: (a) 2D layer viewed along the c-direction, (b) 2D layer viewed along (1, 1j, 0) direction, (c) schematic view of the rationalized (4, 4) topological net, (d) schematic view of the 2D f 3D interpenetrated network containing 1D channel (yellow).

in each copper(I) atom is completed by four iodine atoms or three iodine atoms and one nitrogen atom from Bta- ligand. Each iodine atom adopts either a µ2- or µ3- or µ4- bridging mode. Four pairs of copper(I) atoms in each SBU-II are square-planar

linked to four SBUs-I by four pairs of Cu-N coordinated bonds [Cu-N 2.0090(6) Å]. In SBU-III (Figure 1c), six copper(I) atoms are linked to six µ3-bridged iodide atoms to form a D6R ribbon-shaped ring [Cu-I 2.51028(8)–2.73667(9) Å, Cu · · · Cu 2.67677(8)–2.68044(8) Å]. Each SBU-III is linearly linked to two SBUs-I by two pairs of Cu-N bonds, satisfying a tetrahedral coordination environment of each copper(I) atom. To be noted, both Cu8 and Cu9 are located in two disordered positions with half occupancy and are coordinated by three iodine atoms, adopting a planar-trigonal geometry. SBU-III is different from the reported Cu6Br6 and Cu6I6 clusters,8 in which all copper(I) atoms have tetrahedral coordinated geometry. Adjacent SBU-II extends along the c-direction by SBU-I and extends along the [110] direction by SBU-I-III-I to form a 2D

572 Crystal Growth & Design, Vol. 8, No. 2, 2008

Figure 4. Complex 3: 1D chain containing corrugated double-stranded stairlike [CuI]n chain. Symmetry code: #1 -x + 2, -y + 2, -z + 2, #2 -x + 1, -y + 2, -z + 2.

brick-wall plane with rectangular windows [dimensions 14.0586 (4) × 19.9371(6) Å], which can be rationalized to a (4, 4) topological net by treating SBU-II as a square-planar node and SBU-I/III as a linker (Figure 2c). A very fascinating and peculiar structure feature of 1 is that all 2D sheets parallel to the (1j10) plane are perpendicular to the ones parallel to the (001) plane, resulting in a 2D f 3D interpenetrated topological network (Figure 2d). The interpenetration of two perpendicular 2D sheets

Wu et al.

constructs 1D nanochannels along the c-direction with a void space of 1179.7 Å3 (10.4%) in a unit cell, 15 which are occupied by (DMBta)+ guest cations and I- ions (Figure 3a). A careful examination indicates that all benzene rings of Bta- locate in the perpendicular direction of the channel with the edge of 13.8729(4) Å, and there exist strong infinite π · · · π stacking interactions (3.4221–3.4932 Å) among (DMBta)+ guest cations and Bta- ligands from the anionic host framework (Figure 3b). The structural solution of 1 reveals that disordered iodide atoms exist in the asymmetric unit of 1. As suggested in the formula of 1, we defined one of the iodide atoms as iodide ion and others as iodide molecules due to the charge balance of the whole framework, which is further confirmed by the result of XPS and TGA (Figures S2 and S3, Supporting Information). [Cu2I2(MBta)] (2). Although the single-crystal structure of complex 2 could not be refined properly due to poor reflection data, an preliminary structural solution gives a framework of [Cu2I2(MBta)]. It also contains monoalkylated ligands, similar to the structure of complex 3. [Cu2I2(MTa)] (3). Complex 3 is a polymeric double-stranded stairlike ribbon with the asymmetric unit containing two

Figure 5. Complex 4: (a) 1D [Cu6I5]+ chain along the a-axis, (b) 2D anionic layer with intralayer π · · · π interaction along the (010) direction, (c) 3D packing diagram, showing the alternate arrangement of anionic layers (green) and cationic layers (blue).

Figure 6. Complex 5: (a) 1D [Cu2I]+ chain with square-planar bridging µ4-I atoms, (b) 2D sheet (grey, C; blue, N; red, Cu; purple, I).

Anionic CunIn Cluster-Based Architectures

crystallographically independent copper(I) centers, two iodine ions, and one MTa ligand (Figure 4). All copper(I) atoms adopt distorted tetrahedral coordinated geometry comprised of three iodine atoms and one nitrogen atom from the MTa ligand [Cu–I 2.6024(9)–2.7063(11) Å, Cu–N 2.052(5) Å]. There exist three different Cu · · · Cu diagonal distances [Cu(1)–Cu(1#1) 2.6430(18) Å, Cu(1#1)–Cu(2) 2.8762(12) Å, Cu(2)–Cu(2#2) 2.7178(16) Å]. Cu1 and Cu2 centers are simultaneously bridged by 2- and 3-N of MTa ligand and I1 anions to form zigzag [CuI]n chains oriented in the a direction, and the two [CuI]n chains are linked by Cu–I bonds to form corrugated double-stranded stairlike structure. (Cu5I5)[Cu(Ta)2]- · (DETa)+ (4). Complex 4 consists of alternate arranging anionic 2D layers (A) of {(Cu5I5)[Cu(Ta)2]}and cationic (DETa)+ layers (B). Layer A contains pentamer Cu5I5 cores, in which each of four copper(I) atoms (Cu1, Cu3, Cu4, Cu5) coordinate three iodine atoms and one nitrogen atom from ligand Ta-, and only Cu2 atom is tetrahedrally connected to four iodine atoms [Cu-I 2.573(2)–2.869(2) Å]. The five copper(I) atoms build two opposite slightly distorted triangles by Cu · · · Cu weak interactions with the edges of 2.668(3)– 2.760(3) Å. Adjacent Cu5I5 cores are bridged by sharing I5 to form 1D chain along the b direction (Figure 5a). [Cu(Ta)2]subunits connect adjacent 1D chains by a Cu-I bond [Cu-I 2.88044(3)–2.93485(3) Å] along the c direction to construct a 2D layer (A) (Figure 5b). In [Cu(Ta)2]-, Cu6 is tetrahedrally coordinated to two iodide ions and two 1-N atoms from two Ta- ligands, whose 2- and 3-N atoms coordinate to two copper(I) atoms located in adjacent 1D [Cu6I5]+ chains [Cu-N 1.91557(2)–2.01496(2) Å]. The 2D layers (A) locate alternately parallel to c direction, separated by bulky (DETa)+ guest cation layers (B), and the distance of the interlayer is 10.4275 Å (Figure 5c). An interesting feature of 4 is that the µ2-I2, µ3-I1/I4, µ4-I3, µ5-I5 modes coexist in the compound. According to recent version CSD, only one example of a µ5-I compound is reported,16 and this is the first example bearing four different bridging-mode iodides. [Cu3I(Bta)2] (5). Complex 5 consists of 2D simple sheets with the asymmetric unit containing one crystallographically unique Bta- ligand, half an iodide atom, and one and half copper(I) atoms. The 2D sheet can be regarded as a bilayer structure constructed by a [(Cu2I)+]n chains and [Cu(Bta)2]subunits. In the 1D [(Cu2I)+]n chain, I1 adopts square-planar bridging mode to connect four copper(I) atoms [Cu-I 2.7619(1)–2.8039(1) Å], and Cu1 is tetrahedrally joined to two iodide atoms and two nitrogen atoms from two Bta- ligand (Figure 6a). The completely planar µ4-bridging mode in 5 is different from other reported distorted µ4-bridge examples.17 In the [Cu(Bta)2]- subunit, analogue to SBU-I in 1, Cu2 linearly coordinates two 2-N atoms from two Bta- ligands, whose 1and 3-N atoms link two adjacent [(Cu2I)+]n chains by Cu-N bonds [Cu-N 1.90645(8)–1.94390(9) Å, N-Cu-N 159.219(7)°] to form a 2D sheet (Figure 6b). Conclusions In summary, we have successfully synthesized and characterized five new copper(I) iodide inorganic–organic hybrid coordination polymers based on CuI and in situ N-alkylated triazolium ligands. The new simultaneous in situ N-alkylated and self-assembly reaction affords a highly unusual 2D f 3D interpenetrated porous framework containing two novel neutral discrete Cu10I10/Cu6I6 clusters, which enrich the structure variation of high-nuclear CunIn cluster-based architectures. The import of the in situ generated N-alkylated organic cations is

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possibly an effective way to examine the influence of organic cationic templates on the construction of anionic coordination frameworks. Acknowledgment. The authors gratefully acknowledge the financial support by the National Natural Science Foundation of China (Nos. 20571050 and 20271031) and the Natural Science Foundation of Guangdong Province of China (No. 021240). Supporting Information Available: Crystallographic files in CIF format; figures illustrating ESI-MS analysis spectra of different filtrates, XPS and TGA of complex 1 in PDF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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